Process for the preparation of a functionalized polymer intermediate products, compositions and shaped parts

ABSTRACT

Process for the preparation of a functionalized polymer containing an additive, in which process there is formed a compound that contains, besides at least one blocked isocyanate group, a free amino, hydroxy or carboxy group; this compound is linked to an additive via the free amino, hydroxy or carboxy group in the additive; this additive linked to the compound mentioned is contacted with a polymer that contains at least one free amino or hydroxyl group, at a temperature above the polymer&#39;s melting point and at least above (150)° C., such that the blocked isocyanate group reacts with the free amino or hydroxy group of the polymer to form the functionalized polymer. The invention also relates to the intermediate products formed in the process and in the preparation thereof. Lasdy, the invention relates to functionalized polymers and polymer compositions containing the functionalized polymer.

The invention relates to a process for the preparation of afunctionalised polymer. The invention also relates to intermediateproducts, processes for the preparation thereof, a functionalizedpolymer and a polymer composition containing a functionalized polymer aswell as shaped parts.

A functionalized polymer may be prepared by adding an additive to apolymer. Certain properties of the polymer are improved in this way. Astabilizer, for example, is added in order to improve the stability of apolymer. Additives blended in polymers generally tend to migrate out ofthe polymer. This is also known as the “bleeding” of additives. Anadditive that bleeds out of a polymer accumulates on the surface of thepolymer. This means not only the loss of a valuable additive from thepolymer, but there also develops a deposit on the polymer surface. Sucha deposit on the surface of a polymer is undesirable for manyapplications. Furthermore, the additive, while migrating out of thepolymer, may cause deposits in polymer processing equipment. Ininjection moulding of polymers, for example, the additive may deposit ina mould. As a consequence, the injection moulding operation needs to beinterrupted in order to clean the mould. Such interruptions ofproduction processes are undesirable from a cost viewpoint.

Furthermore, additives may bleed out of coatings. Additives that areadded to a coating composition or paint may migrate to the surface. As aresult, the performance of the additive present on the surface may belost, which is undesirable.

In a known method of preparing a functionalized polymer, the molecularweight of the additive is first increased and then the additive isblended in a polymer. This reduces the bleeding of additives out ofpolymers.

Another manner of preparing functionalized polymers is described byWolfe in Rubber Chemistry and Technology (vol. 54, p. 988-995). Here,during the polymerization of segmented polyether ester elastomers,antioxidants are co-polymerized by utilizing bifunctional monomers withantioxidant properties, in this application also referrred to asantioxidant. This prevents the antioxidant from bleeding out of thepolymer. Dimethyl5-(3,5-di-t-butyl4-hydroxybenzenepropanamido)-isophthalate, among othersubstances, is mentioned as a bifunctional antioxidant.

A drawback of this method as described by Wolfe is that it can only beapplied during the polymerization of the polymer.

The invention aims to provide a process for the preparation offunctionalized polymers that is not limited to the polymerization of thepolymer and that prevents the additive from migrating.

This is achieved according to the invention in that

-   a. a first compound, containing at least one primary amino group and    at least a group chosen from a first series comprising a secondary    amino group, an amino group on a secondary carbon atom and a primary    hydroxyl group or a group chosen from a second series comprising a    hydroxyl group on a secondary carbon atom and a carboxy group, or a    first compound containing at least one group chosen from the first    series and also contains at least a group chosen from the second    series whereby optionally said first or second series furthermore    comprise a double or triple bond, is contacted with an amount of    carbonylbislactam (CBL) at a temperature below 150° C. and with the    amount of carbonyl bislactam being at least equimolar to the number    of primary amino groups or at least equimolar to the number of    groups chosen from the first series and with the molar amount of    carbonyl bislactam being lower than the sum of the molar number of    primary amino groups and groups chosen from the first or second    series or lower than the sum of the molar number of groups chosen    from the first series and chosen from the second series, as a result    of which a first intermediate compound is formed which contains,    besides at least one blocked isocyanate group, a free amino,    hydroxy, carboxy group or a double or triple bond;-   b. the first intermediate compound is contacted, at a temperature    preferably below 150° C., with an additive such that a link is    established via the free amino, hydroxy, carboxy group or the double    or triple bond, resulting in the formation of a second intermediate    compound;-   c. the second intermediate compound is contacted with a polymer    having at least one free amino group or hydroxyl group at a    temperature above the melting point of the polymer and at least    above 150° C., such that the blocked isocyanate group reacts with    the free amino or hydroxy group of the polymer to form the    functionalized polymer.

The invention provides a process for the preparation of functionalizedpolymers, which process is not limited to the polymerization of thispolymer and prevents an additive from bleeding. Large amounts of polymerare usually continuously produced during polymerization. This means thatwhen an additive is added during the polymerization of the polymer,large amounts of a functionalized polymer, comprising said additive, areproduced. The process according to the invention allows smaller batchesof functionalised polymer to be produced more easily in, for example, acompounding process. By adding an additive not during polymerization butlater, for example during compounding in an extruder or during injectionmoulding in an injection moulding machine, greater flexibility isobtained than during the production of a polymer or a polymercomposition. In addition, the continuous polymerization process is notdisturbed in this manner.

In the process according to the invention a first reaction is carriedout as mentioned under a. By way of an example of a first reaction, areaction A) is shown below, in which a first compound, I, contains twoprimary amine groups and a secondary amine group and in whichcarbonylbiscaprolactam, CBC, is used as exemplary CBL. In reactionequation A), the first compound reacts with two moles of CBC to form thefirst intermediatecompound, II, with two moles of caprolactam beingsplit off.

The reaction may be carried out ‘in bulk’, with the compound having thesecondary amine, hydroxy or carboxy group and the CBL being contacteddirectly, but the reaction may also be carried out in solution.

A catalyst may optionally be applied in order to accelerate thereaction. Preferably a catalyst is applied for a reaction with ahydroxyl group. In that case the reaction is significantly accelerated.Suitable catalysts include acids, including Lewis acids, and bases,including Lewis bases.

Examples of acids, including Lewis acids, that are suitable as acatalyst are LiX, Sb₂O_(3,) GeO₂ en As₂O₃, BX₃, MgX₂, BiX₃, SnX₄, SbX₅,FeX₃, GeX₄, GaX₃, HgX₂, ZnX₂, AlX₃, TiX₄, MnX₂, ZrX₄, R₄NX, R4PX, HX,where X=I, Br, Cl, F, OR, acetylacetonate, or a compound according toformula (a)

in which formula R″ and R′″ are independently chosen from the seriescomprising alkyl, aryl, alkoxy and aryloxy. and R=alkyl or aryl.Brönstedt acids such as H₂SO₄, HNO₃, HX′ (where X′=I, Br, Cl, F), H₃PO₄,H₃PO₃, RH₂PO₂, RH₂PO₃, R[(CO)OH]_(n), where n=1-6 are also suitable.

Examples of bases, including Lewis bases, that are suitable as acatalyst are MH_(n), M(OH)_(n), (R′O)_(n)M (M=Alkali or earth alkali,R′=alkyl with C₁-C₂₀ or aryl), NR′_(n)H_(4-n)OH (R′=alkyl with C₁-C₂₀ oraryl), triamines such as triethylamine, tributyl amine, trihexylamine,trioctylamine and cyclic amines such as diazobicyclo[2,2,2]octane(DABCO), dimethylaminopyridine (DMAP), guanidine, morfoline.

It is also possible to accelerate the reaction in the presence ofanother compound such as an acid scavenger.

If a solvent is used, preferrably an aprotic solvent is used. Thisprevents unwanted reactions with the solvent. Suitable aprotic solventsare for example aliphatic or aromatic hydrocarbons such as toluene orxylene.

The reaction of step a. of the invention is carried out at a temperaturebelow 150° C. Undesirable side reactions may take place above 150° C.,potentially resulting in a compound with less or no blocked isocyanteanymore. The reaction is preferably carried out at a temperature below125° C. If the boiling point of the chosen solvent is lower than thedesired reaction temperature, the reaction may, if desired, be carriedout under pressure and/or reflux. In general the reaction is carried outat a temperature above room temperature, preferably above 50° C. Longreaction times are prevented in this manner. A suitable first compoundis one containing at least one primary amino group and at least a groupchosen from a first series comprising a secondary amino group, an aminogroup on a secondary carbon atom, a primary hydroxyl group or a groupchosen from a second series comprising a hydroxyl group on a secondarycarbon atom and a carboxy group, or a first compound containing at leastone group chosen from the first series and also at least one groupchosen from the second series. The chosen groups may be mutually bondedby one or more aliphatic, cycloaliphatic or aromatic units chosenindependently of one another.

Examples of suitable first compounds are for examplebishexamethylenetriamine, bisethylenetriamine, bispropylenetriamine,2-(ethylamino)ethylamine, 3-(methylamino)propylamine,3-(cylohexylamino)propylamine, 1,2-propanediamine,N,N′-1,2-ethanediylbis-(1,3-propanediamine), N-(aminoethyl)benzylamine.Examples of a first compound containing amino and hydroxy groups are forexample ethanolamine, propanolamine, isopropanolamine,2-(2-aminoethyoxy)ethanol, N-(2-aminoethyl)ethanolamine,N-methylethanolamine, diethanolamine, chitin. Further examples of afirst compound comprising a primary hydroxy group and a hydroxy group ona secondary carbon atom are glycerol, 1,2-pentanediol,1,2,4-butanetriolor glucose. Examples of first compounds containing amino and carboxygroups are glycine, asparagine, lysine, glutamine or γ-aminocapronicacid.

Various types may be used as CBL. Preferably carbonylbiscaprolactam,CBC, is used because of its commercial availability.

In the reaction of the invention referred to under b., the firstintermediate compound is contacted, preferably at a temperature below150° C., with an additive such that a link is established via the freeamino, hydroxy or carboxy group or via a double or triple bond to form asecond intermediate compound. The additive's linkage to the firstintermediate compound takes place via a reactive group that is presenton the additive. An example of this link is shown in the reactionequation B) below, which is based on the reaction product of reaction A)and wherein YFn symbolizes the additive containing a reactive group Y.If the first intermediate compound contains several reactive groups permolecule, then several molecules of the additive per molecule of thefirst intermediate compound may be linked.

The linkage may take place if the additive contains a reactive group Ycapable of reacting directly with a group of the first intermediatecompound. Reactive groups on the additive may be an amino, hydroxyl orcarboxy group, or a halide, an ester, an isocyanate, an epoxy, analdehyde or an anhydride. In some cases the linkage cannot take placedirectly, for example because both the first intermediate compound andthe additive contain groups that do not react directly with one another,for example when both contain a hydroxyl, amino or carboxy group. Insuch cases the linkage may take place via a so-called linking unit. Thislinking unit contains one reactive group capable of reacting with thereactive group of the first intermediate compound and one reactive groupcapable of reacting with the reactive group present in the additive. Ifthe linking unit is to link with a hydroxyl group, the linking unitpreferably contains an acid group, an isocyanate, a dihalogenide or acyclic anhydride. If the linking unit is to link with an amino group, itpreferably contains an acid group, an isocyanate, an aldehyde or acyclic anhydride, or carbonylbislactam. In using this latter compoundthe reaction has to be carried out at a temperature above 150° C. If thelinking unit is to link with a carboxy group, it preferably contains anamino group or hydroxy group. Suitable linking units may be cyclicanhydrides, diisocyanates or aldehydes.

Examples of cyclic anhydrides are for example succinic anhydride, maleicanhydride or phthalic anhydride. A diisocyanate that may be suitable isfor example isoferondiisocyanate (IPDI) or toluenediisocyanate (TDI).Examples of aldehydes are for example formaldehyde, acetaldehyde,benzaldehyde or glyoxal. If a linking unit is used, it is preferablyfirst reacted with the first intermediate compound or the additive andthe formed product is subsequently, in a next reaction step, reactedwith the additive or the first intermediate compound respectively.

An additive in this invention is understood to be an antioxidant, aflame retardant, a bactericide, a fungicide, a dying agent, asurfactant, an anti-fouling agent, a colouring agent, an antistaticagent or a lubricant, or a combination thereof.

The reaction is preferably carried out at a temperature below 150° C.,because otherwise undesirable side reactions may take place. In generalthe reaction is carried out at a temperature above room temperature,preferably above 50° C. Long reaction times are prevented in thismanner.

In the reaction referred to under c. above, the second intermediatecompound is contacted with a polymer having at least one free aminogroup or hydroxyl group such that the blocked isocyanate group of thesecond intermediate compound reacts with the free amino group or hydroxygroup of the polymer. In the process according to the invention thesecond intermediate compound is preferably added to the polymer in anextruder or injection moulding machine. In this manner, the secondintermediate compound is rapidly blended with the polymer and a quickreaction takes place at the high temperatures during extrusion orinjection moulding. Under these conditions the reaction will usually becomplete in a few minutes. The second intermediate compound may also beadded during the production of coating compositions. The secondintermediate compound may be metered directly to the extruder or may beadded to the extruder or injection moulding machine pre-blended with thepolymer or other additives. If the second intermediate compound isliquid, it may also be added to the extruder or injection mouldingmachine with a liquid metering system. It is also possible to addadditives that react with acid groups, if present, such asphenylenebisoxazoline, phenylenebisoxazine, (di)epoxides andcarbodiimides. During the reaction of the blocked isocyanate group ofthe second intermediate compound with a free amino or hydroxy group ofthe polymer caprolactam is split off, which caprolactam may be removedfrom the extruder or injection moulding machine or polymer throughdevolatization.

If the second intermediate compound contains one blocked isocyanategroup, the second intermediate compound may be linked to the end of thepolymer chain. If the second intermediate compound contains severalblocked isocyanate groups, it may also be incorporated in the polymer.If the second intermediate compound links two polymer chains, chainextension may occur. This is manifested by an increase in the molar massof the polymer. An extra advantage of the invention is that additiveshaving only one functional group may also be used. In the publication byWolfe cited above this is not possible since the addition of amonofunctional compound during the polymerization may result in chaintermination, as a result of which the polymer's molecular mass islimited. Also, the addition, via the process of the invention, of theadditives cited by Wolfe will not result in a functionalized polymer inwhich additives do not bleed, since in general the additives cited byWolfe react only slowly. Consequently, over the relatively shortreaction time in an extruder, practically no reaction takes place withthe polymer, so allowing the additives still to bleed out of thepolymer.

The second intermediate compound is contacted with the polymercontaining at least one free amino or hydroxy group at a temperatureabove the melting point of the polymer and at least at 150° C. At lowertemperatures the reaction will proceed more slowly and will not run tocompletion during the residence time in the extruder. The uppertemperature limit is not subject to any further limitation than thetemperature customary for melt processing of the polymers in question.

Polymers that contain a free amino or hydroxy group are for examplepolyamides, polyesters, copolyesters, polyethers, polyacrylates,cellulose and amine or hydroxy functionalized polymers or copolymers orblends thereof.

Exemplary polyamides are polyamides and copolyamides that are derivedfrom diamines and dicarboxylic acids and/or from aminocarboxylic acidsor the corresponding lactams, such as polyamide 4, polyamide 6,polyamide 11, polyamide 12, polyamide 6/6, 4/6, partially aromatic(co)polyamides, for example polyamides based on an aromatic diamine andadipic acid; polyamides produced from an alkylenediamine and isophthalicand/or terephthalic acid and copolyamides thereof.

Exemplary polyesters are polyesters derived from dicarboxylic acids ase.g terephthalic acid, isophthalic acid and trimellitic acid, anddialcohols as e.g. ethylene glycol, propane diol, butanediol, neopentylglycol and/or from hydroxycarboxylic acids or the corresponding lactonesincluding polyethyleneterephthalate, polypropyleneterephthalate,polybutyleneterephthalate, poly-1,4-dimethylolcyclohexaneterephthalate,polycaprolacton and copolyesters thereof or thermosetting polyestersderived of any one of the above mentioned monomers.

Exemplary polyethers are polytetrahydrofuran, polypropyleneglycol,polyethyleneglycol and polyoxymethylene and copolyethers thereof orcopolymers containing the abovementioned polyesters, in particularcopolyesters including Arnitel®.

Examples of amine functionalized polymers are for example aminefunctionalized polyethers including Jeffamines and amino terminatedacrylonitrilebutadiene copolymers (ATBN).

An exemplary hydroxy functionalized polymer is for examplehydroxyfunctional polybutadiene.

The amount of the second intermediate compound to be added to thepolymer may be freely chosen. Preferably the amount of the additive ischosen to be equal to or lower than the amount of free amino or hydroxygroups. These groups may be determined by techniques known to thoseskilled in the art. In general, a polymer with a lower molar masscontains more free amino or of hydroxy groups so that a larger amount ofthe second intermediate compound may be linked to a polymer with a lowermolar mass. The amount of the second intermediate compound is preferablyso chosen that the amount of additive to be introduced in the polymer isequal to the desired dosage of the additive in the polymer composition.If a larger amount of additive is to be added to the polymer via thesecond intermediate compound than the available terminal groups in thispolymer, this may be accomplished by using a second intermediatecompound to each molecule of which more than one molecule of theadditive is linked.

If desired, fillers may be added during compounding. In general, theremay be added glass fibres, glass spheres, glass lamellae, mineralfillers including for example, mica, talcum, chalk or gypsum, rubbers,including for example halogenated polymer systems and synergists such asantimonetrioxide, sodiumantimonate or zinc borate.

The invention also relates to a first intermediate compound comprisingat least one blocked isocyanate group and a free amino, hydroxy orcarboxy group.

The invention further relates to a second intermediate compoundcomprising an additive that is linked to a compound containing at leastone blocked isocyanate group. In this second intermediate compound theadditive may be linked to the first intermediate compound via the freeamino, hydroxy or carboxy group or via a double or triple bond presentin the first intermediate compound.

Furthermore, the invention relates to a process for obtaining the saidintermediate compounds and product. It concerns a process for thepreparation of the first intermediate compound, wherein the processcomprises step a. of the process of the invention. In this process theadditive is chosen from the series of stabilizers, flame retardants,bactericides, fungicides, dying agents, surfactants, anti-foulingagents, colouring agents, antistatic agents and lubricants.

The invention further relates to a process for the preparation of thesecond intermediate compound wherein the process comprises stepsmentioned under a. and b. of the process of the invention. The inventionfurther relates to an alternative route to produce a functionalisedpolymer using an additive comprising a lactam blocked isocyanate groups.Such process comprises

-   a. reacting an additive comprising at least one amino group or a    hydroxyl group with carbonylbislactam at a temperature below 150° C.    such that a link is established via the amino group or hydroxyl    group of the additive, thereby forming an intermediate product A,-   b. contacting the intermediate product A with a polymer having at    least one free amino group or hydroxyl group at a temperature above    the melting point of the polymer and at least above 150° C., such    that the blocked isocyanate group reacts with the free amino group    or hydroxy group of the polymer to form a functionalized polymer.

In this process an intermediate product A is formed. The inventiontherefore also relates to an intermediate product A comprising anadditive provided with a lactam blocked isocyanate group as well as theprocess for the preparation of an intermediate product A, whichcomprises step a. of the above mentioned alternative process accordingto the invention.

In the case of intermediate product A which contains only one blockedisocyanate, an additive comprising an amino group or a hydroxyl group isreacted with CBL at a temperature preferably below 150° C., with saidadditive such that a link is established via the amino group or hydroxylgroup of the additive.

The invention also provides a functionalised polymer obtainable by theprocess of the invention.

Such a functionalized polymer may also be added to other polymers, thisgroup of other polymers not necessarily being limited to the group ofpolymers that contain a free amino or hydroxy group. The inventiontherefore also provides polymer compositions containing also afunctionalized polymer with an additive that does not bleed.

Said functionalized polymers or polymer compositions according to theinvention can also be applied in coating compositions. The inventiontherefore also provides a coating composition comprising functionalizedpolymers according to the invention or shaped articles comprising afunctionalised polymer composition according to the invention Thecoating composition can further comprise the usual fillers applied incoating chemistry.

Upon curing of the coating composition according to the invention acoating is obtained on a substrate. The invention therefore furthermoreprovides substrates comprising a coating based on the coatingcomposition according to the invention.

Furthermore the invention relates to shaped articles comprisingfunctionalized polymers according to the invention or shaped articlescomprising functionalised polymer compositions according to theinvention. The shaped articles can be produced by the known methods ase.g. injection moulding or extrusion. Consequently shaped articlescomprise moulded parts extruded parts, films, strapping and fibres.

The invention is elucidated by the following non-limiting examples.

EXAMPLE I

Preparation of a First Intermediate Ompound Containing an Amino Groupand Two Blocked Isocyanate Groups

10.3 g (0.1 mol) of bisethylenetriamine and 50.4 g (0.2 mol) ofcarbonylbiscaprolactam (CBC) are dissolved in 100 ml of toluene. Thesolution is heated to 70° C. for 1 hour. After the mixture has cooleddown to room temperature, caprolactam liberated in the reaction isextracted twice with 50 ml of water. The product, the caprolactamblocked diisocyanate of bisethylenetriamine, has formed virtuallyquantitatively and can be isolated by distilling off toluene.

EXAMPLE II

Preparation of a First Intermediate Ompound Containing an Amino Groupand Two Blocked Isocyanate Groups

21.5 g (0.1 mol) of bishexamethylenetriamine and 50.4 g (0.2 mol) ofcarbonylbiscaprolactam (CBC) are dissolved in 100 ml of toluene. Thesolution is heated to 70° C. for 1 hour. After the mixture has cooleddown to room temperature, caprolactam liberated in the reaction isextracted twice with 50 ml of water. The product, the caprolactamblocked diisocyanate of bishexamethylenetriamine, has formed virtuallyquantitatively and can be isolated by distilling off toluene.

EXAMPLE III

Preparation of an Intermediate Product A Containing an Amino Group andOne Blocked Isocyanate Ground

15.0 g (0.1 mol) of (2-aminoethyl) benzylamine and 25.2 g (0.1 mol) ofcarbonylbiscaprolactam (CBC) are dissolved in 100 ml of toluene. Thesolution is heated to 70° C. for 1 hour. After the mixture has cooleddown to room temperature, caprolactam liberated in the reaction isextracted twice with 50 ml of water. The product, the caprolactamblocked mono-isocyanate of (2-aminoethyl) benzylamine, has formedvirtually quantitatively and can be isolated by distilling off toluene.

EXAMPLE IV

Preparation of an Intermediate Product A Containing an Amino Group andOne Blocked Isocyanate Group

16.8 g (0.1 mol) of 1,1-dimethyl, 3,3-dimethyl, 5-aminopiperidine and25.2 g (0.1 mol) of carbonylbiscaprolactam (CBC) are dissolved in 100 mlof toluene. The solution is heated to 70° C. for 1 hour. After themixture has cooled down to room temperature, caprolactam liberated inthe reaction is extracted twice with 50 ml of water. The product, thecaprolactam blocked mono-isocyanate of 1,1-dimetyl, 3,3-dimethyl,5-aminopiperidine, has formed virtually quantitatively and can beisolated by distilling off toluene

EXAMPLE V

Preparation of a Second Intermediate Compound that Contains the AdditiveDimethylphosphite Linked to the Fist Intermediate Compound in Example Ivia a Formaldehyde Linking Unit

91.9 g (0.25 mol) of caprolactam blocked diisocyanate ofbisethylenetriamine (obtained in Example I), 7.5 g of formaldehyde (0.25mol) as a linking unit and 100 ml of methanol are heated to 60° C. for 1hour. In a second step 27.5 g (0.25 mol) of the additivedimethylphosphite are added in the presence of 0.5 g of NaOH as acatalyst. After two hours the excess of methanol is distilled off andthe product is washed once with 50 ml of water. The product is aphosphorus modified caprolactam blocked diisocyanate ofbisethylenetriamine, that cab be used to prepare a flame retardantpolymer that dos not bleed.

EXAMPLE VI

Preparation of a Second Intermediate Compound that Contains an Additive,the Acid Chloride of Perfluorododecanoic Carboxylic Acid, Linked to theFirst Intermediate of Example I via an Amino Group

91.9 g (0.25 mol) of caprolactam blocked diisocyanate ofbisethylenetriamine (see Example I) and 25 g (0.25 mol) of triethylamine(as acid scavenger) are dissolved in 400 ml of toluene. A solution of158 g (0.25 mol) of the additive, the acid chloride ofperfluordodecanoic carboxylic acid, in 200 ml of toluene, is added atroom temperature. After that, the solution is heated to 40° C. for 2hours. Next, the formed triethylamine.HCl salt is filtered off and thefiltrate is concentrated by evaporation. The product is the amide ofperfluorododecanoic carboxylic acid and the caprolactam blockeddiisocyanate of bisethylenetriamine, which can be used to form afunctionalised polymer with a built in fouling agent.

EXAMPLE VII

Preparation of a Functionalized Polymer

A mixture of 5 wt % of the phosphorus modified caprolactam blockeddiisocyanate of bisethylenetriamine as obtained in Example V and 95 wt %of nylon-6 are added to the hopper of an extruder. The extrudertemperature is adjusted to 260° C. and the residence time is approx. 2minutes. The strands of the polymer composition thus obtained arechopped to form a granulate. The granulate is processed in an injectionmoulding machine at 260° C. and a mould temperature of 85° C. into testbars of 3*6*75 mm and tested in terms of flame retardance through LOI,limiting oxygen index. The LOI of the test bars was measured to ASTMD2863 and amounted to 26. This is substantially higher than that of testbars obtained without the compound in Example V, where the LOI amountedto 21. While injection moulding 500 test bars, the mould did not exhibitany deposit from the phosphorus compound bleeding out of the polymer.

EXAMPLE VIII

Preparation of an Intermediate Product A Comprising One CaprolactamBlocked Isocyanate Group and a Fluorine Containing Additive.

A commercially available per-fluorine alkyl alcohol (see reaction below,n=7) was reacted with carbonyl biscaprolactam in equimolar amounts inthe presence of MgBr₂ as catalyst for two hours at 125° C., according tothe reaction below.

EXAMPLE IX

Preparation of Coating Comprising the Additive of Example VIII on aSubstrate

A coating composition was made by blending a hydroxy functionalpolyester resin according to the following formulaC₂H₅C[CH₂{OC(O)RC(O)O(CH₂)_(n)O}_(m)H]₃in which n=4 and m=1, the per-fluorine alkyl blocked isocyanate ofexample VIII, and a tri-functional blocked isocyanate Desmodur® BL-3272(Bayer). The overall OH/NCO molar ratio was maintained slightly higherthan 1. The ratio of per-fluorine alkyl blocked isocyanate to BL-3272was chosen such that the fluorine content was 3% by weight of the film.The coating composition was applied on clean aluminum panels in such anamount as to obtain a coating thickness of about 20 μm and then cured at200° C. for 0.5 hour. The thickness of the cured coating on thealuminium substrate was found to be 20 μm, as measured using aTwin-Check thickness gauge by List-Magnetic GmbH. Contact angles weremeasured with deionized water and hexadexane (>99%, Merck) on a contactangle microscope (G10, Krüss, Hamburg-Germany) and amounted to 80° and125° with hexadexane and water, respectively. From these contact anglessurface energy of the coating was calculated according to methods knownto the skilled man. This surface energy of the coating was 9 mN/m, whichis significantly lower that the surface energy of 40 mN/m measured atthe same coating not comprising the intermediate product A of ExampleVIII. The fact that the surface energy of the coating was very low canalso be seen by comparing with the value for Teflon, which was measuredto be 20 mN/m. The coating according to the invention therefore has alower surface energy than Teflon which is well known for its low surfaceenergy. Due to the low surface energy of the coating of 9 mN/m, thecoating showed very good anti fouling and non staining properties.

Furthermore extraction tests were done with aceton to verify whether theintermediate product A of Example VIII could be removed from thecoating. It was not possible to remove the intermediate product A ofexample VIII from the coating through the aceton treatment. Thus theintermediate product A of example VIII is chemically fixed at thecoating.

EXAMPLE X

Preparation of Functionalised Polymer Comprising the IntermediateProduct A of Example IV

The additive as obtained through Example IV was fed to a twinscrewextruder of diameter 30 mm together with polyamide 6, (PA6). The amountof the intermediate product A of Example IV was 0.7% by weight of theamount of polyamide 6. The temperature of the extruder barrel was set to265° C. and a functionalized polymer was obtained upon meltmixing thePA6 with the intermediate product A of Example IV. After leaving theextruder, the functionalized polymer was cut into pellets and dried to amoisture amount of less than 0.05 w %.

Of the dried polymer fibers were spun and compared with that of apolyamide 6, not comprising the intermediate product A according toExample IV. It was seen that the melt degradation of the polymerobtained according to Example X, upon melt processing, was less thanthat of a polyamide 6, not comprising the intermediate product Aaccording to Example IV. Dyability of the fibres of both the polyamide 6with or without the intermediate product A of Example IV werecomparable.

1. Process for the preparation of a functionalized polymer wherein a. afirst compound, containing at least a primary amino group and at least agroup chosen from a first series comprising a secondary amino group, anamino group attached to a secondary carbon atom and a primary hydroxylgroup or a group chosen from a second series comprising a hydroxyl groupattached to a secondary carbon atom and a carboxy group, or a firstcompound containing at least a group chosen from the first series andalso contains at least a group chosen from the second series wherebyoptionally said first or second series furthermore comprise a double ortriple bond, is contacted with an amount of carbonyl bislactam at atemperature below 150° C. and with the amount of carbonyl bislactambeing at least equimolar to the number of primary amino groups or atleast equimolar to the number of groups chosen from the first series andwith the molar amount of carbonyl bislactam being lower than the sum ofthe molar number of primary amino groups and groups chosen from thefirst or second series or lower than the sum of the molar number ofgroups chosen from the first series and chosen from the second series,as a result of which a first intermediate compound is formed whichcontains, besides at least one blocked isocyanate group, a free aminogroup, hydroxy group, carboxy group or a double or triple bond; b. thefirst intermediate compound is contacted, at a temperature preferablybelow 150° C., with an additive such that a link is established via thefree amino, hydroxy or carboxy group or via a double or triple bond toform a second intermediate compound. c. the second intermediate compoundis contacted with a polymer having at least one free amino group orhydroxyl group at a temperature above the melting point of the polymerand at least above 150° C., such that the blocked isocyanate groupreacts with the free amino group or hydroxy group of the polymer to formthe functionalized polymer.
 2. Process according to claim 1 wherein thecarbonylbislactam is carbonylbiscaprolactam.
 3. Process according toclaim 1 wherein the polymer is chosen from the series of polyamides,polyesters, copolyesters, polyethers, polyacrylates, cellulose andhydroxy or amino functionalized polymers.
 4. First intermediate compoundcomprising at least one blocked isocyanate group and a free amino,hydroxy or carboxy group, or a double or triple bond.
 5. Process for thepreparation of the compound of claim 4, wherein: a. a first compound,containing at least a primary amino group and at least a group chosenfrom a first series comprising a secondary amino group, an amino groupattached to a secondary carbon atom and a primary hydroxyl group or agroup chosen from a second series comprising a hydroxyl group attachedto a secondary carbon atom and a carboxy group, or a first compoundcontaining at least a group chosen from the first series and alsocontains at least a group chosen from the second series wherebyoptionally said first or second series furthermore comprise a double ortriple bond, is contacted with an amount of carbonyl bislactam at atemperature below 150° C. and with the amount of carbonyl bislactambeing at least equimolar to the number of primary amino groups or atleast equimolar to the number of groups chosen from the first series andwith the molar amount of carbonyl bislactam being lower than the sum ofthe molar number of primary amino groups and groups chosen from thefirst or second series or lower than the sum of the molar number ofgroups chosen from the first series and chosen from the second series,as a result of which a first intermediate compound is formed whichcontains, besides at least one blocked isocyanate group, a free aminogroup, hydroxy group, carboxy group or a double or triple bond; b. thefirst intermediate compound is contacted, at a temperature preferablybelow 150° C., with an additive such that a link is established via thefree amino, hydroxy or carboxy group or via a double or triple bond toform a second intermediate compound.
 6. Second intermediate compoundcomprising an additive that is linked to the first intermediate compoundin claim 4 via the free amino, hydroxy or carboxy group, or a double ortriple bond present in the first intermediate compound.
 7. Secondintermediate compound according to claim 6 wherein the additive ischosen from the series of stabilizers, flame retardants, bactericides,fungicides, surfactants, anti-fouling agents, colouring agents,antistatic agents and lubricants.
 8. Process for the preparation of thesecond intermediate compound of claim 6 wherein: a. a first compound,containing at least a primary amino group and at least a group chosenfrom a first series comprising a secondary amino group, an amino groupattached to a secondary carbon atom and a primary hydroxyl group or agroup chosen from a second series comprising a hydroxyl group attachedto a secondary carbon atom and a carboxy group, or a first compoundcontaining at least a group chosen from the first series and alsocontains at least a group chosen from the second series wherebyoptionally said first or second series furthermore comprise a double ortriple bond, is contacted with an amount of carbonyl bislactam at atemperature below 150° C. and with the amount of carbonyl bislactambeing at least equimolar to the number of primary amino groups or atleast equimolar to the number of groups chosen from the first series andwith the molar amount of carbonyl bislactam being lower than the sum ofthe molar number of primary amino groups and groups chosen from thefirst or second series or lower than the sum of the molar number ofgroups chosen from the first series and chosen from the second series,as a result of which a first intermediate compound is formed whichcontains, besides at least one blocked isocyanate group, a free aminogroup, hydroxy group, carboxy group or a double or triple bond. 9.Process for the preparation of a functionalized polymer by a. reactingan additive comprising at least one amino group or a hydroxyl group withcarbonylbislactam at a temperature below 150° C. such that a link isestablished via the amino group or hydroxyl group of the additive,thereby forming an intermediate product A, b. contacting theintermediate product A with a polymer having at least one free aminogroup or hydroxyl group at a temperature above the melting point of thepolymer and at least above 150° C., such that the blocked isocyanategroup reacts with the free amino group or hydroxy group of the polymerto form a functionalized polymer.
 10. Intermediate product A comprisingan additive provided with a lactam blocked isocyanate group.
 11. Processfor the preparation of an intermediate product A according to claim 10,wherein: a. reacting an additive comprising at least one amino group ora hydroxyl group with carbonylbislactam at a temperature below 150° C.such that a link is established via the amino group or hydroxyl group ofthe additive, thereby forming an intermediate product A. 12.Functionalized polymer obtainable according to the process of claim 1.13. Polymer composition containing a functionalized polymer according toclaim
 12. 14. Shaped article comprising the polymer composition of claim13.
 15. Shaped article according to claim 14 wherein the shaped articleis a film, fibre, monofilament or strapping.
 16. Coating compositioncomprising the second intermediate compound of claim
 6. 17. Substratecomprising a coating based on the coating composition according to claim16.
 18. Coating composition comprising the second intermediate compoundof claim 7.